CN103849466A - Weather-proof migration-proof long-acting type microcapsule essence and preparation method thereof - Google Patents
Weather-proof migration-proof long-acting type microcapsule essence and preparation method thereof Download PDFInfo
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- CN103849466A CN103849466A CN201410129123.5A CN201410129123A CN103849466A CN 103849466 A CN103849466 A CN 103849466A CN 201410129123 A CN201410129123 A CN 201410129123A CN 103849466 A CN103849466 A CN 103849466A
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- polyvinyl alcohol
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- aminoresin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 70
- 229920003180 amino resin Polymers 0.000 claims abstract description 49
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 20
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 20
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a weather-proof migration-proof long-acting type microcapsule essence and a preparation method thereof. An oil soluble essence oil is used as a capsule core, and a first wall material layer, a second wall material layer and a third wall material layer are sequentially coated outside the capsule core from inside to outside, the first wall material layer is a terpolymer of gelatin, Arabic gum and carboxymethylcellulose, with a thickness of 0.5-1.5 mu m; the second layer material layer is an amino resin polymer, with a thickness of 1-3 mu m; and the third wall material layer is a polyvinyl alcohol compound with a thickness of 0.5-1.5 mu m. The microcapsule essence disclosed by the invention is a powdery product with good liquidity, and particle size distribution of 1-15 mu m, and is uniformly dispersed in a high polymer material and good in weather resistance and migration resistance. The decompsotion temperature and the softening temperature of the microcapsule essence disclosed by the invention can be about 240 DEG C; and the microcapsule essence is firm in capsule material, and can not be greatly broken in an extrusion molding process.
Description
One, technical field
The present invention relates to a kind of micro encapsulation essence and preparation method thereof, specifically a kind of weather-proof long-acting type of resistance to migration microcapsule essence and preparation method thereof.
Two, background technology
Essence is by the imitation fruit of synthetic and the concentrated perfume oil of natural perfume smell, it is a kind of synthetic flavour, it can covering smell, discharge the comfortable smell of pleasant, as lemon oil can produce refreshing effect to the mind, increase work efficiency, jasmine oil is consoled, analgesic activity, and rose oil (rose oil) is consoled and relexation etc.Essence is mostly liquid material, and the fragrant time of high volatility and guarantor is short, and poor heat resistance, can not be directly used in macromolecular material.Although existing coated method can improve the resistance toheat of essence microcapsule, but the macromolecular material product containing its additive only can be used for indoor scenarios, fragrance remaining time also, mostly at 2-6 month, also exists weathering resistance poor, additive easily moves to the problems such as material surface, and can not be used for outdoor.
Nowadays the range of application of thermoplastic macromolecule material in people's daily life is more and more wider, and a lot of manufacturers are experienced in order to improve product identification and user, are chosen in material and add essence to attract clients.Due to the weathering resistance that exterior material is had relatively high expectations, make it very high to the requirement of essence additive, wherein typical example is exactly artificial lawn.Artificial lawn is the grass silk that the materials such as nylon, polypropylene, polyethylene are pulled into, and by knitting together with careless machine is sewn to, and then by butadiene-styrene rubber, both is bonded together with polypropylene lattice cloth.The advantage such as chinampa has that outward appearance is bright-coloured, the four seasons are evergreen, color is lively, drainage performance is good, long service life, maintenance cost are low.But because lawn is exposed to outdoor, under the condition be exposed to the sun at sunlight, rain drop erosion, difference variation being violent, existing essence microcapsule weathering resistance and poor air-tightness, fragrance remaining time under occasion is short out of doors, the consistency of Shell Materials and base material is poor, there is mechanical properties decrease and migration problem, can not meet the requirement that outdoor occasion is used.
Three, summary of the invention
The present invention aims to provide a kind of weather-proof long-acting type of resistance to migration microcapsule essence and preparation method thereof, and technical problem to be solved is to improve fragrance remaining time and the resistance to elevated temperatures of microcapsule essence, and has weathering resistance and resistance to migration.Microcapsule essence of the present invention is particularly useful for preparing the essence microcapsule of strong volatility essence and the weather-proof long-acting type of the resistance to migration essence microcapsule for outdoor goods material.
The weather-proof long-acting type of the resistance to migration microcapsule essence of the present invention, is taking oily perfume essential oil as capsule-core, is coated with successively from the inside to the outside the first layer wall material, second layer wall material and the 3rd layer of wall material in capsule-core outside;
Described the first layer wall material is the terpolymer of gelatin, gum arabic and carboxymethyl cellulose, and thickness is 0.5 μ m-1.5 μ m;
Described second layer wall material is aminoresin polymkeric substance, and thickness is 1 μ m-3 μ m;
Described the 3rd layer of wall material is polyvinyl alcohol mixture, and thickness is 0.5 μ m-1.5 μ m;
Between described the first layer wall material and described second layer wall material, be connected by the grafting of twain-aldehyde compound material; Between described second layer wall material and described the 3rd layer of wall material, be connected by the grafting of twain-aldehyde compound material;
The raw material of described microcapsule essence is configured to by mass percentage:
Described aminoresin class material is selected from one or more in trimeric cyanamide, urea, phenyl guanamine, is preferably trimeric cyanamide;
Described twain-aldehyde compound material is selected from one or more in glutaraldehyde, hexanedial, mda, suceinic aldehyde, is preferably glutaraldehyde;
Described polyvinyl alcohol material is selected from one or more in polyvinyl alcohol 2699, polyvinyl alcohol 2399, polyvinyl alcohol 1799, polyvinyl alcohol 1788, preferably polyethylene alcohol 2699, polyvinyl alcohol 2399 or polyvinyl alcohol 1799;
Described trifunctional hydroxy kind linking agent is selected from one or more in TriMethylolPropane(TMP), tri hydroxy methyl butane, trimethylolethane, is preferably TriMethylolPropane(TMP) or tri hydroxy methyl butane.
The mass ratio of carboxymethyl cellulose and gum arabic is 1-2:1, is preferably 1:1;
The quality of trifunctional hydroxy kind linking agent is the 5%-10% of polyvinyl alcohol material mass, is preferably 5%.
The preparation method of the weather-proof long-acting type of the resistance to migration microcapsule essence of the present invention, comprises that pre-polymerization, emulsion dispersion, microcapsule coated, polyvinyl alcohol are coated and the each unit process of aftertreatment:
Described pre-polymerization is that the formaldehyde of the twain-aldehyde compound material of aminoresin class material, 10-20%, 75-90% is mixed with water, stir, with the sodium hydroxide solution adjust pH of mass concentration 5% be 8-9, be warming up to 60-75 DEG C of reaction, react to reaction solution clarification and be incubated 30-60min, then add gelatin to continue insulation 30-60 minute, obtain aminoresin mixed prepolymer; The twain-aldehyde compound material of 10-20% refers to that the twain-aldehyde compound material adding in this step is the 10-20% of twain-aldehyde compound raw material of substance quality, and the formaldehyde of 75-90% refers to that the formaldehyde adding in this step is the 75-90% of formaldehyde raw material quality, lower same.In pre-collecting process, the mol ratio of aminoresin class material and aldehyde radical is preferably 1:1-5; The formaldehyde that wherein molar weight of aldehyde radical is added in this step and total aldehyde radical of twain-aldehyde compound material.
Described emulsion dispersion is that oily perfume essential oil, carboxymethyl cellulose and gum arabic are added to the water, and carries out homogenizing emulsifying in 25-50 DEG C, obtains essence emulsion;
Described microcapsule coated is to regulate the pH value of essence emulsion to 4.6-5.5 by buffered soln, then under 30-50 DEG C of stirring, drip the aminoresin mixed prepolymer of 30-40%, time for adding is controlled at 1-2 hour, after dripping off, regulate the pH value of essence emulsion to 4.2-5.0 by buffered soln, under 30-50 DEG C of stirring, drip the aminoresin mixed prepolymer of 30-40%, time for adding is controlled at 1-2 hour, after dripping off, regulate the pH value of essence emulsion to 3.8-4.8 by buffered soln, under 30-50 DEG C of stirring, drip the aminoresin mixed prepolymer of surplus, time for adding is controlled at 1-2 hour, after dripping off, pass through buffered soln adjust pH 3.5-4.5, insulated and stirred reaction 1-2 hour, then be warming up to 65-85 DEG C of insulation reaction 4-6 hour, described buffered soln is the mixed aqueous solution of one or more materials in sodium-chlor, Repone K, ammonium chloride, acetic acid, citric acid, hydrogenchloride, primary ammonium phosphate, Sodium phosphate dibasic, and the pH value of buffered soln is 3.0-5.3, adding sodium-chlor or Repone K is in order to produce salting out, to carry the high clad ratio of microcapsule,
Described polyvinyl alcohol is coated is that the temperature of the reaction solution obtaining after microcapsule coated is adjusted to 30-50 DEG C, regulate pH value to 2.5-3.5 by the HCl solution of mass concentration 5%, then add polyvinyl alcohol material, trifunctional hydroxy kind linking agent, the formaldehyde of surplus and the twain-aldehyde compound material of surplus, insulated and stirred reaction 5-7 hour; In the coated process of polyvinyl alcohol, the mass ratio of polyvinyl alcohol material, formaldehyde and twain-aldehyde compound material is preferably 4-12:1:3-11, wherein formaldehyde and twain-aldehyde compound material refer to the formaldehyde and the twain-aldehyde compound material that in this step, add, i.e. the twain-aldehyde compound material of the formaldehyde of surplus and surplus.
Described aftertreatment is the pH value to 7 of the reaction solution that obtains after the NaOH solution by mass concentration 5% regulates polyvinyl alcohol coated, filters, washs also obtained microcapsule essence after 30-50 DEG C of oven drying 12-24 hour.
In pre-collecting process the quality of water be aminoresin class material mass 15-25 doubly;
In emulsion dispersion process the quality of water be oily perfume essential oil quality 20-25 doubly.
Optimization of preparation is:
Described pre-polymerization is that aminoresin class material, 14% twain-aldehyde compound material and 85% formaldehyde are mixed with water, stir, with the sodium hydroxide solution adjust pH of mass concentration 5% be 9, be warming up to 70 DEG C of reactions, react to reaction solution clarification and be incubated 30min, then add gelatin to continue insulation 30 minutes, obtain aminoresin mixed prepolymer.
Described microcapsule coated is the pH value to 4.6 that regulates essence emulsion by buffered soln, then under 50 DEG C of stirrings, drip 40% aminoresin mixed prepolymer, time for adding 1 hour, after dripping off, regulate the pH value to 4.2 of essence emulsion by buffered soln, under 50 DEG C of stirrings, drip 30% aminoresin mixed prepolymer, time for adding 1 hour, after dripping off, regulate the pH value to 3.8 of essence emulsion by buffered soln, under 50 DEG C of stirrings, drip the aminoresin mixed prepolymer of surplus, time for adding 1 hour, after dripping off, pass through buffered soln adjust pH 3.5, insulated and stirred reaction 1 hour, then be warming up to 65 DEG C of insulation reaction 4 hours, described buffered soln is the mixed aqueous solution of sodium-chlor, ammonium chloride, acetic acid, hydrogenchloride, primary ammonium phosphate, in buffered soln, the mass concentration of sodium-chlor is 5%, the mass concentration of ammonium chloride is 5%, the mass concentration of acetic acid is 3%, the mass concentration of hydrogenchloride is 0.3%, the mass concentration of primary ammonium phosphate is 5%, and the pH value of buffered soln is 3.2.
Described polyvinyl alcohol is coated is that the temperature of the reaction solution obtaining after microcapsule coated is adjusted to 50 DEG C, HCl solution by mass concentration 5% regulates pH value to 2.5, then add polyvinyl alcohol material, trifunctional hydroxy kind linking agent, the formaldehyde of surplus and the twain-aldehyde compound material of surplus, insulated and stirred reaction 6 hours.
Microcapsule essence of the present invention is taking oily perfume essential oil as capsule-core; Taking gelatin gum arabic-carboxymethyl cellulose complex coacervation thing as the first layer wall material, using melamine formaldehyde resin (melmac) as second layer wall material, taking polyvinyl alcohol as the 3rd layer of wall material, between the first layer wall material and second layer wall material, connect by glutaraldehyde grafting, between second layer wall material and the 3rd layer of wall material, connect by glutaraldehyde grafting.
In the first layer wall material, can there is complex coacervation in gelatin and gum arabic, gelatin and carboxymethyl cellulose under specific pH value, and its speed of response is fast, agglomerated product is charging property not, easily be combined with core, clad ratio is high, but its mechanical property, resistance toheat and air-tightness are all very limited.The Main Function of the first layer wall material is on oily perfume essential oil oil droplet, to be coated rapidly the even shell of one deck, and curing oil droplet prevents that it from merging again.The consistency of the first layer wall material and oily perfume essential oil is good, is conducive to fixing oily perfume essential oil drop, improves clad ratio, carries out basis for the later stage is coated.Because its speed of response is fast, capsule material clad ratio is high, and the complex coacervation thing of generation is with net charge amount low, and therefore surface deposition has the essence essential oil oil droplet surface electrostatic repulsive force of condensation product to reduce, and melmac can be coated uniformly on the first layer housing.
In second layer wall material, melmac, owing to having good thermotolerance and mechanical stability, is therefore widely used in the aspects such as furniture vehicle building, although its mechanical property is good, and resistance to air loss, poor with consistency and the processing characteristics of non-polar polymeric material.In the preparation process of second layer wall material, the present invention is added dropwise to aminoresin mixed prepolymer in the mode of buffered soln segmentation control pH value, and the material of participating in reaction all generates capsule material, and raw material availability is high.Melmac is owing to having thermoset, and the Main Function of its housing is the thermotolerance that improves microcapsule, solidifies housing framework, the frictional force while making microcapsule hold out against extrusion molding and shearing force.
In the 3rd layer of wall material, polyvinyl alcohol (PVA) oil resistant, resistance to solvent, outstanding to gas barrier property, aspect food, medicine and packaging, there is unique advantage, and the consistency of itself and macromolecular material is good, be difficult for migration.As can be seen here, three's advantage can extraordinary mutual enhancing and is made up.Polyvinyl alcohol in the 3rd layer of wall material is connected with the formaldehyde grafting in second layer wall material by glutaraldehyde, forms polyvinyl alcohol-glutaraldehyde-formaldehyde composite cross-linked polymer, and this composite cross-linked polymer can improve housing toughness, extends the slow-release time of essence.Because polyvinyl alcohol has special resistance to air loss, in significantly extending slow-release time, also can accomplish steadily slowly discharging of essence, rate of release long term maintenance is in same level.In addition, polyvinyl alcohol and various thermoplastic macromolecule material consistency are good, and resistance to migration can make microcapsule essence be embedded in for a long time macromolecular material deep layer, further improves essence sustained release performance.
In the preparation process of microcapsule essence, if using melmac as the first layer housing, because its wall material need to form by prepolymer condensation curing, a large amount of essence oil droplets can again merge in condensation curing process, therefore capsule material clad ratio is lower, makes flavor of raw material loss serious; If make it as the 3rd layer of housing, because the molecular chain of aminoresin prepolymer is not as the molecular chain length of polyvinyl alcohol, microcapsule coated need to be consumed to a large amount of aminoresin raw materials, cost is increased, and the distinctive stickiness of polyvinyl alcohol can cause the extremely inhomogeneous of aminoresin condensation curing, easily cause a large amount of clusters and empty bag.Through repetition test, find that melmac is all fine to the consistency of complex coacervation thing (the first layer wall material) and polyvinyl alcohol (the 3rd layer of wall material), and consistency between complex coacervation thing and polyvinyl alcohol is very poor.Therefore melmac is the most suitable as second layer housing.
Although if using polyvinyl alcohol as the first layer or second layer housing can be coated more even, its good resistance to air loss make essence be difficult to volatilization, cause microcapsule fragrance deficiency.When a large amount of polyvinyl alcohol raw material, add and also can make the viscosity of reaction solution too high, make the easy bonding cluster of product cause separation difficulty, and the conditional request pH value of polyvinyl alcohol generation aldol condensation is minimum, the later stage is continued into shell also to be needed to regulate pH value, and it is industrial unfavorable to cause.Therefore polyvinyl alcohol is the most suitable as the 3rd layer of housing.
If using complex coacervation thing (the first layer wall material) as the second layer or the 3rd layer of wall material, because the intensity of charge bonded is lower, can cause declining to a great extent of casing rigidity, the increase of capsule-core causes housing raw materials cost very high, also be difficult to regulation and control in the complex coacervation reaction response speed compared with under high concentration of feed, and show general mechanical property and air-tightness and have little significance as strengthening housing by it.Therefore complex coacervation thing is the most suitable as the first layer housing.
The emulsifying dispersant of the present invention using carboxymethyl cellulose as oily perfume, its consumption is little, and under the acting in conjunction of machinery and emulsifying dispersant, the stable essence dispersion that can make narrow diameter distribution is, to coated very favourable.Aminoresin mixed prepolymer contains gelatin, as pH, gelatin can be with positive charge during lower than certain value, with electronegative carboxymethyl cellulose generation electrostatic interaction, generate condensation product with very fast speed of response, before essence oil droplet merges again by its parcel, condensation product is with net charge amount to reduce, therefore surface deposition has the volatile oil bead surface electrostatic repulsion forces of condensation product to reduce, easily adhered to by melmac prepolymer, form larger spherical multinuclear microcapsule, for the later stage second, multilayer shell is coated lays a good foundation.
But because carboxymethyl cellulose is the macromolecular compound of the straight chain rigidity that a kind of molecular structure is single, there is shortcoming in gelatin-carboxymethyl cellulose condensation product therefore on viscosity, be difficult to be coated on fully the surface of essence oil droplet, therefore need modification.Gum arabic is a kind of mixture being made up of saccharan and protein sugar etc., and it has good stickiness, and can with gelatin generation complex coacervation.Therefore in the time of emulsion dispersion, add a certain amount of gum arabic, it not only can play the effect of emulsifying dispersant, also can jointly react and generate the complex coacervation thing that stickiness is higher with gelatin and carboxymethyl cellulose, with this, degree of reliability coated the first layer housing is strengthened greatly, the glutaraldehyde in prepolymer and formaldehyde also can improve degree of crosslinking and the clad ratio of complex coacervation.
The synthetic of melmac can be divided into two stages: the one, and in the methylolation stage, trimeric cyanamide reacts under alkaline environment with formaldehyde and generates methylolation trimeric cyanamide prepolymer; The 2nd, in the polycondensation stage, there is polycondensation in melamine methylol prepolymer under sour environment, forms water-fast crosslinking structure polymkeric substance.In prepolymerization reaction, add glutaraldehyde, its contained two aldehyde radicals, an aldehyde radical replaces formaldehyde to react with trimeric cyanamide, glutaraldehyde is embedded in the middle of melmac housing, another aldehyde radical part is reacted with the polyvinyl alcohol in the 3rd layer of wall material, cross-linking polyvinyl alcohol-glutaraldehyde-methanal complex, with these grafting two, three two layers of walls materials.Remaining part aldehyde radical with the first layer wall material in amino generation amine aldehyde condensation reaction in gelatin, multiple molecule crosslinked network structures are formed, thereby make together with gelatin gum arabic-carboxymethyl cellulose complex coacervation thing housing is closely adhered to melmac housing, to reach the effect of grafting.
On polyvinyl alcohol, contain a large amount of hydroxyls, can with glutaraldehyde and formaldehyde generation aldol reaction.Under the modification of trifunctional hydroxy kind linking agent, glutaraldehyde can be by the polyvinyl alcohol crosslinked reticulated structure that becomes of straight chain shape, together with also can polyvinyl alcohol composite cross-linked polymer being grafted on melmac housing by unnecessary aldehyde radical.But the consumption of glutaraldehyde can not be too much, otherwise can make a large amount of polyvinyl alcohol generation self-crosslinkings, clad ratio is declined, and glutaraldehyde consumption can make the hydroxyl on polyvinyl alcohol can not get abundant reaction very little, makes coated imprecision, housing easily breaks.Therefore, use appropriate glutaraldehyde, and add formaldehyde and carry out modification, make hydroxyl generation aldol reaction adjacent on polyvinyl alcohol, to fill up cancellated vacancy, resistance to air loss and the mechanical property of balance polyvinyl alcohol shell.Due to formaldehyde or the raw material of the coated process of melmac, this method can make starting material be fully used, and reduces free formaldehyde content.
The present invention is that use gelatin gum arabic-carboxymethyl cellulose complex coacervation thing is the 3rd layer of wall material as the first layer wall material, melmac as second layer wall material, polyvinyl alcohol, between three layers of wall material, by chemical bond grafting, jointly form multilayer shell oily perfume essential oil is carried out to multilayer coating structure.Multilayer capsule material of the present invention uses in order, the high clad ratio that has not only obtained complex coacervation with become shell speed, also retain mechanical property and the resistance toheat of melmac, maintained again good resistance to air loss and the consistency of polyvinyl alcohol, the range of application of essence microcapsule can be improved greatly.Microcapsule essence of the present invention is white mobility powder, be easy to disperse in macromolecular material, size distribution between 1-15 μ m and according to demand situation is adjusted, microcapsule essence smooth surface, between particle without adhesion, profile is round or ellipse particle under the microscope, heat resisting temperature is more than 240 DEG C, add the outdoor actual measurement lasting of artificial lawn duration within 1 month, to extend to more than 12 months from the deficiency of existing product, add EVA foaming plate slow-release indoor lasting duration to extend to more than 24 months.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the decomposition temperature of microcapsule essence of the present invention and softening temperature all can reach 240 DEG C of left and right, and capsule material is firm, and capsule does not occur to break on a large scale in extrusion process.
2, the powdery product that product of the present invention is good fluidity, size distribution is at 1-15 μ m, and easily dispersed in macromolecular material, weathering resistance and resistance to migration are good.
3, the product application that the present invention makes (addition 2.0%) in the curling grass silk of polypropylene of artificial lawn is placed in open air, still maintains fragrance after 12 months.Temper(ing) case was tested after one week, and it is good that material mechanical performance keeps, and did not have microcapsule essence migration and surface to ooze out phenomenon.
4, the product application that the present invention makes (addition 1.5%) in ethylene-vinyl acetate copolymer sheet material is placed in indoor, after 24 months, still maintains fragrance.
Four, brief description of the drawings
The micro encapsulation essence of embodiment 1-3 and comparative example 1 is carried out slowly-releasing contrast by Fig. 1, the baking oven inner dryings of 70 DEG C 336 hours, and the rate of release of the essence recording.In Fig. 1, transverse axis is the time, and the longitudinal axis is the quality of residue essence.The initial evaporation rate of visible comparative example 1 is very fast, about the 9th hour, evaporation rate starts to decline to a great extent, and about 100 hours, just release is complete substantially for its essence, and that the release rate of 3 groups of embodiment is stablized is moderate, substantially can accomplish that whole process all has fragrance and discharges, still savory while end to experiment.
Fig. 2 and Fig. 3 are the scanning electron microscope Photomicrograph that the embodiment of the present invention 1 is prepared microcapsule, show that capsule grain diameter size is more even in figure, about 10 μ m left and right.
Fig. 4 and Fig. 5 are the light micrograph that the embodiment of the present invention 1 is prepared microcapsule, show that capsule grain diameter size is more even in figure, can see obvious clad structure.
Fig. 6 is the embodiment of the present invention 1 and the thermogravimetric analysis comparison diagram of comparative example 1, and during as seen from Figure 6 since 120 DEG C, comparative example 1 is weightless rapidly, volatilized 91.5% and start decomposition, and the weightlessness of embodiment 1 obviously slows down when 190 DEG C of left and right.
Five, embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
1, pre-polymerization
Add the formalin of 5.0g trimeric cyanamide, 9.0g mass concentration 37%, the suceinic aldehyde aqueous solution and the 100.0g water of 0.8g mass concentration 50% to being equipped with in the 500ml there-necked flask of thermometer, agitator and reflux condensing tube, with the sodium hydroxide solution adjust pH 9 of mass concentration 5%, be warmed up to 70 DEG C of reactions, react to reaction solution clarification and be incubated 0.5 hour, then add 1.0g gelatin to continue insulation reaction 0.5 hour, make aminoresin mixed prepolymer solution, be down to 50 DEG C for subsequent use.
2, emulsion dispersion
In 500ml beaker, add successively 300.0g water, 0.4g carboxymethyl cellulose and 0.35g gum arabic, open homogeneous emulsifying machine (model ESR, Shanghai Sample Model Factory), add 12.5g lemon enriching essence (above Hailin handkerchief spices company limited), emulsion dispersion 20 minutes at 50 DEG C, make essence emulsion, for subsequent use.
3, microcapsule coated
The essence emulsion that step 2 is made joins thermometer is housed, in the 500ml four-hole boiling flask of agitator and reflux condensing tube and dropping funnel, regulate the pH value to 5.4 of essence emulsion with the HCl solution of mass concentration 5%, 30% the aminoresin mixed prepolymer solution that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off the rear HCl solution by mass concentration 5% and regulate pH value to 5.0, 30% the aminoresin mixed prepolymer solution that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off the rear HCl solution by mass concentration 5% and regulate pH value to 4.5, the aminoresin mixed prepolymer solution of the surplus that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off the rear HCl solution by mass concentration 5% and regulate pH value to 4.0, insulation reaction 1 hour, then be warming up to 75 DEG C of insulation reaction 4 hours.
4, polyvinyl alcohol is coated
The temperature of the reaction solution obtaining after microcapsule coated is adjusted to 50 DEG C, HCl solution by mass concentration 5% regulates pH value to 2.5, then add 4.0g polyvinyl alcohol 1799,0.4g TriMethylolPropane(TMP), the formalin of 2.0g mass concentration 37%, the suceinic aldehyde aqueous solution of 6.0g mass concentration 50%, insulated and stirred reaction 5 hours;
5, aftertreatment
The pH value to 7 of the reaction solution that the NaOH solution by mass concentration 5% obtains after regulating polyvinyl alcohol coated, is cooled to room temperature, filters, washing obtain microcapsule essence after being dried 12 hours in 50 DEG C.
Embodiment 2:
1, pre-polymerization
Add the formalin of 3.0g trimeric cyanamide, 1.9g phenyl guanamine, 8.5g mass concentration 37%, the suceinic aldehyde aqueous solution and the 90.0g water of 1.0g mass concentration 50% to being equipped with in the 500ml there-necked flask of thermometer, agitator and reflux condensing tube, with the sodium hydroxide solution adjust pH 9 of mass concentration 5%, be warmed up to 70 DEG C of reactions, react to reaction solution clarification and be incubated 0.5 hour, then add 0.8g gelatin to continue insulation reaction 0.5 hour, make aminoresin mixed prepolymer solution, be down to 50 DEG C for subsequent use.
2, emulsion dispersion
In 500ml beaker, add successively 280.0g water, 0.5g carboxymethyl cellulose and 0.4g gum arabic, open homogeneous emulsifying machine (model ESR, Shanghai Sample Model Factory), add 14g lemon enriching essence (above Hailin handkerchief spices company limited), emulsion dispersion 10 minutes under room temperature, make essence emulsion, for subsequent use.
3, microcapsule coated
The essence emulsion that step 2 is made joins thermometer is housed, in the 500ml four-hole boiling flask of agitator and reflux condensing tube and dropping funnel, regulate the pH value to 5.5 of essence emulsion with buffered soln, 33% the aminoresin mixed prepolymer solution that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off rear by buffered soln adjusting pH value to 5.0, 33% the aminoresin mixed prepolymer solution that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off rear by buffered soln adjusting pH value to 4.4, the aminoresin mixed prepolymer solution of the surplus that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off rear by buffered soln adjusting pH value to 3.5, insulation reaction 1 hour, then be warming up to 65 DEG C of insulation reaction 4 hours.
Buffered soln is the mixed aqueous solution of sodium-chlor, ammonium chloride, acetic acid, hydrogenchloride, primary ammonium phosphate, in buffered soln, the mass concentration of sodium-chlor is 5%, the mass concentration of ammonium chloride is 5%, the mass concentration of acetic acid is 3%, the mass concentration of hydrogenchloride is 0.3%, the mass concentration of primary ammonium phosphate is 5%, and the pH value of buffered soln is 3.2.
4, polyvinyl alcohol is coated
The temperature of the reaction solution obtaining after microcapsule coated is adjusted to 50 DEG C, HCl solution by mass concentration 5% regulates pH value to 3, then add 4.0g polyvinyl alcohol 2399,0.35g tri hydroxy methyl butane, the formalin of 2.5g mass concentration 37%, the suceinic aldehyde aqueous solution of 7.0g mass concentration 50%, insulated and stirred reaction 6 hours;
5, aftertreatment
The pH value to 7 of the reaction solution that the NaOH solution by mass concentration 5% obtains after regulating polyvinyl alcohol coated, is cooled to room temperature, filters, washing obtain microcapsule essence after being dried 24 hours in 50 DEG C.
Embodiment 3:
1, pre-polymerization
Add the formalin of 4.5g urea, 8.0g mass concentration 37%, glutaraldehyde water solution and the 100.0g water of 1.0g mass concentration 50% to being equipped with in the 500ml there-necked flask of thermometer, agitator and reflux condensing tube, with the sodium hydroxide solution adjust pH 9 of mass concentration 5%, be warmed up to 70 DEG C of reactions, react to reaction solution clarification and be incubated 0.5 hour, then add 0.8g gelatin to continue insulation reaction 0.5 hour, make aminoresin mixed prepolymer solution, be down to 50 DEG C for subsequent use.
2, emulsion dispersion
In 500ml beaker, add successively 240.0g water, 0.34g carboxymethyl cellulose and 0.32g gum arabic, open homogeneous emulsifying machine (model ESR, Shanghai Sample Model Factory), add 12.0g lemon enriching essence (above Hailin handkerchief spices company limited), emulsion dispersion 30 minutes under room temperature, make essence emulsion, for subsequent use.
3, microcapsule coated
The essence emulsion that step 2 is made joins thermometer is housed, in the 500ml four-hole boiling flask of agitator and reflux condensing tube and dropping funnel, regulate the pH value to 4.6 of essence emulsion with buffered soln, 33% the aminoresin mixed prepolymer solution that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off rear by buffered soln adjusting pH value to 4.2, 33% the aminoresin mixed prepolymer solution that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off rear by buffered soln adjusting pH value to 4.0, the aminoresin mixed prepolymer solution of the surplus that step 1 is made drops in reactor at 50 DEG C, time for adding is 1 hour, drip off rear by buffered soln adjusting pH value to 3.5, insulation reaction 1 hour, then be warming up to 65 DEG C of insulation reaction 3 hours.
Buffered soln is the mixed aqueous solution of Repone K, ammonium chloride, acetic acid, hydrogenchloride, primary ammonium phosphate, in buffered soln, the mass concentration of Repone K is 5%, the mass concentration of ammonium chloride is 5%, the mass concentration of acetic acid is 3%, the mass concentration of hydrogenchloride is 0.3%, the mass concentration of primary ammonium phosphate is 6%, and the pH value of buffered soln is 3.0.
4, polyvinyl alcohol is coated
The temperature of the reaction solution obtaining after microcapsule coated is adjusted to 50 DEG C, HCl solution by mass concentration 5% regulates pH value to 2.5, then add 4.0g polyvinyl alcohol 2699,0.4g TriMethylolPropane(TMP), the formalin of 1.0g mass concentration 37%, the glutaraldehyde water solution of 7.5g mass concentration 50%, insulated and stirred reaction 6 hours;
5, aftertreatment
The pH value to 7 of the reaction solution that the NaOH solution by mass concentration 5% obtains after regulating polyvinyl alcohol coated, is cooled to room temperature, filters, washing obtain microcapsule essence after being dried 24 hours in 50 DEG C.
Comparative example 1:
1, pre-polymerization: to the formalin and the 130.0g water that add 6.4g trimeric cyanamide, 12.5g mass concentration 37% in the 500ml there-necked flask of thermometer, agitator and reflux condensing tube are housed, with the sodium hydroxide solution adjust pH to 9 of mass concentration 5%, be warmed up to 70 DEG C, the transparent rear insulation reaction of reaction solution 0.5 hour, make aminoresin prepolymer solution, be down to room temperature for subsequent use.
2, emulsion dispersion: add 200.0g water and 10.0g lemon enriching essence (above Hailin handkerchief spices company limited) and 0.3g carboxymethyl cellulose in 500ml beaker, open homogeneous emulsifying machine (model ESR, Shanghai Sample Model Factory), emulsion dispersion 30 minutes under room temperature, make essence emulsion, for subsequent use.
3, microcapsule coated: above-mentioned essence emulsion and aminoresin prepolymer are joined in the 500ml there-necked flask that thermometer, agitator and reflux condensing tube are housed, be warming up to 50 DEG C, with the salt acid for adjusting pH value to 4.5 of mass concentration 5%, react 4 hours, be then warming up to 60 DEG C and continue reaction 4 hours; After finishing, reaction is cooled to room temperature, with the sodium hydroxide solution adjust pH to 7 of mass concentration 5%.
4, filter, washing, 50 DEG C are dried 24 hours, make white caking shape micro encapsulation essence product.
The micro encapsulation essence of embodiment 1-3 and comparative example 1 is contrasted, and result is as following table:
The product of embodiment 1-3 and comparative example is added in the curling grass silk of the polypropylene of artificial lawn (addition 2.0%), be positioned over outdoorly, simulate under field conditions (factors) actual service condition.
The product of embodiment 1-3 and comparative example is added to (addition 1.5%) in ethylene-vinyl acetate copolymer sheet material, be positioned over indoorly, at room temperature simulate actual service condition.
Claims (10)
1. the weather-proof long-acting type of a resistance to migration microcapsule essence, is characterized in that:
Described microcapsule essence is taking oily perfume essential oil as capsule-core, is coated with successively from the inside to the outside the first layer wall material, second layer wall material and the 3rd layer of wall material in capsule-core outside;
Described the first layer wall material is the terpolymer of gelatin, gum arabic and carboxymethyl cellulose, and thickness is 0.5 μ m-1.5 μ m;
Described second layer wall material is aminoresin polymkeric substance, and thickness is 1 μ m-3 μ m;
Described the 3rd layer of wall material is polyvinyl alcohol mixture, and thickness is 0.5 μ m-1.5 μ m;
Between described the first layer wall material and described second layer wall material, be connected by the grafting of twain-aldehyde compound material; Between described second layer wall material and described the 3rd layer of wall material, be connected by the grafting of twain-aldehyde compound material;
The raw material of described microcapsule essence is configured to by mass percentage:
2. microcapsule essence according to claim 1, is characterized in that:
Described aminoresin class material is selected from one or more in trimeric cyanamide, urea, phenyl guanamine;
Described twain-aldehyde compound material is selected from one or more in glutaraldehyde, hexanedial, mda, suceinic aldehyde;
Described polyvinyl alcohol material is selected from one or more in polyvinyl alcohol 2699, polyvinyl alcohol 2399, polyvinyl alcohol 1799, polyvinyl alcohol 1788;
Described trifunctional hydroxy kind linking agent is selected from one or more in TriMethylolPropane(TMP), tri hydroxy methyl butane, trimethylolethane.
3. microcapsule essence according to claim 1 and 2, is characterized in that:
Described aminoresin class material is trimeric cyanamide;
Described twain-aldehyde compound material is glutaraldehyde;
Described polyvinyl alcohol material is selected from polyvinyl alcohol 2699, polyvinyl alcohol 2399 or polyvinyl alcohol 1799;
Described trifunctional hydroxy kind linking agent is TriMethylolPropane(TMP) or tri hydroxy methyl butane.
4. microcapsule essence according to claim 1, is characterized in that:
The mass ratio of carboxymethyl cellulose and gum arabic is 1-2:1;
The quality of trifunctional hydroxy kind linking agent is the 5%-10% of polyvinyl alcohol material mass.
5. a preparation method for the weather-proof long-acting type of resistance to migration microcapsule essence claimed in claim 1, comprises that pre-polymerization, emulsion dispersion, microcapsule coated, polyvinyl alcohol are coated and the each unit process of aftertreatment:
Described pre-polymerization is that the formaldehyde of the twain-aldehyde compound material of aminoresin class material, 10-20%, 75-90% is mixed with water, stir, with the sodium hydroxide solution adjust pH of mass concentration 5% be 8-9, be warming up to 60-75 DEG C of reaction, react to reaction solution clarification and be incubated 30-60min, then add gelatin to continue insulation 30-60 minute, obtain aminoresin mixed prepolymer;
Described emulsion dispersion is that oily perfume essential oil, carboxymethyl cellulose and gum arabic are added to the water, and carries out homogenizing emulsifying in 25-50 DEG C, obtains essence emulsion;
Described microcapsule coated is to regulate the pH value of essence emulsion to 4.6-5.5 by buffered soln, then under 30-50 DEG C of stirring, drip the aminoresin mixed prepolymer of 30-40%, time for adding is controlled at 1-2 hour, after dripping off, regulate the pH value of essence emulsion to 4.2-5.0 by buffered soln, under 30-50 DEG C of stirring, drip the aminoresin mixed prepolymer of 30-40%, time for adding is controlled at 1-2 hour, after dripping off, regulate the pH value of essence emulsion to 3.8-4.8 by buffered soln, under 30-50 DEG C of stirring, drip the aminoresin mixed prepolymer of surplus, time for adding is controlled at 1-2 hour, after dripping off, pass through buffered soln adjust pH 3.5-4.5, insulated and stirred reaction 1-2 hour, then be warming up to 65-85 DEG C of insulation reaction 4-6 hour, described buffered soln is the mixed aqueous solution of one or more materials in sodium-chlor, Repone K, ammonium chloride, acetic acid, citric acid, hydrogenchloride, primary ammonium phosphate, Sodium phosphate dibasic, and the pH value of buffered soln is 3.0-5.3,
Described polyvinyl alcohol is coated is that the temperature of the reaction solution obtaining after microcapsule coated is adjusted to 30-50 DEG C, regulate pH value to 2.5-3.5 by the HCl solution of mass concentration 5%, then add polyvinyl alcohol material, trifunctional hydroxy kind linking agent, the formaldehyde of surplus and the twain-aldehyde compound material of surplus, insulated and stirred reaction 5-7 hour;
Described aftertreatment is the pH value to 7 of the reaction solution that obtains after the NaOH solution by mass concentration 5% regulates polyvinyl alcohol coated, filters, washs also obtained microcapsule essence after 30-50 DEG C of oven drying 12-24 hour.
6. preparation method according to claim 5, is characterized in that:
In pre-collecting process the quality of water be aminoresin class material mass 15-25 doubly;
In emulsion dispersion process the quality of water be oily perfume essential oil quality 20-25 doubly.
7. preparation method according to claim 5, is characterized in that:
In pre-collecting process, the mol ratio of aminoresin class material and aldehyde radical is 1:1-5;
In the coated process of polyvinyl alcohol, the mass ratio of polyvinyl alcohol material, formaldehyde and twain-aldehyde compound material is 4-12:1:3-11.
8. preparation method according to claim 5, is characterized in that:
Described pre-polymerization is that aminoresin class material, 14% twain-aldehyde compound material and 85% formaldehyde are mixed with water, stir, with the sodium hydroxide solution adjust pH of mass concentration 5% be 9, be warming up to 70 DEG C of reactions, react to reaction solution clarification and be incubated 30min, then add gelatin to continue insulation 30 minutes, obtain aminoresin mixed prepolymer.
9. preparation method according to claim 5, is characterized in that:
Described microcapsule coated is the pH value to 4.6 that regulates essence emulsion by buffered soln, then under 50 DEG C of stirrings, drip 40% aminoresin mixed prepolymer, time for adding 1 hour, after dripping off, regulate the pH value to 4.2 of essence emulsion by buffered soln, under 50 DEG C of stirrings, drip 30% aminoresin mixed prepolymer, time for adding 1 hour, after dripping off, regulate the pH value to 3.8 of essence emulsion by buffered soln, under 50 DEG C of stirrings, drip the aminoresin mixed prepolymer of surplus, time for adding 1 hour, after dripping off, pass through buffered soln adjust pH 3.5, insulated and stirred reaction 1 hour, then be warming up to 65 DEG C of insulation reaction 4 hours, described buffered soln is the mixed aqueous solution of sodium-chlor, ammonium chloride, acetic acid, hydrogenchloride, primary ammonium phosphate, in buffered soln, the mass concentration of sodium-chlor is 5%, the mass concentration of ammonium chloride is 5%, the mass concentration of acetic acid is 3%, the mass concentration of hydrogenchloride is 0.3%, the mass concentration of primary ammonium phosphate is 5%, and the pH value of buffered soln is 3.2.
10. preparation method according to claim 5, is characterized in that:
Described polyvinyl alcohol is coated is that the temperature of the reaction solution obtaining after microcapsule coated is adjusted to 50 DEG C, HCl solution by mass concentration 5% regulates pH value to 2.5, then add polyvinyl alcohol material, trifunctional hydroxy kind linking agent, the formaldehyde of surplus and the twain-aldehyde compound material of surplus, insulated and stirred reaction 6 hours.
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| CN113019273B (en) * | 2021-03-15 | 2022-06-17 | 成都工业学院 | Fragrance sustained-release capsule and preparation method thereof |
| CN114307887A (en) * | 2021-06-10 | 2022-04-12 | 广州昆特臣香精香料科技有限公司 | Preparation method of oily essence microcapsule and microcapsule thereof |
| CN114307887B (en) * | 2021-06-10 | 2023-03-10 | 广州昆特臣香精香料科技有限公司 | Preparation method of oily essence microcapsule and microcapsule thereof |
| CN115024508B (en) * | 2022-05-07 | 2024-06-04 | 江苏万腾新材料科技有限公司 | Capsule wall material with oily essence interlayer and preparation method thereof |
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